Disazo beta resorcylic acid dyestuffs



United States Patent O 3,251,822 DISAZO BETA RESORCYLIC ACID DYESTUFFS Ernest M. May, Summit, and Andrew Fono, Montclair, N.J., assignors to Otto B. May, Ind, Newark, N.J., a corporation of New Jersey No Drawing. Filed Aug. 30, 1962, Ser. No. 220,568 '10 Claims. (Cl. 260-187) classes of dyes have not been entirely suitable since the articles dyed therefrom have had a relative poor fastness to light, washing or dry cleaning, or they have had inadequate brilliance.

An object of the present invention is to obtain dye compositions which are suitable for dyeing polypropylene and other polyolefins to provide an end product with superior fastness properties and with excellent brilliance andtinctorial value.

Another object of the invention is to obtain dyes which can be used for dyeing other thermoplastic resins, such as polyesters, polyacrylics, and polyamides to forrna dyed article having excellent fastness to light, washing and dry cleaning and having exceptional brilliance.

It is a common practice in the textile industry to form composite fabrics containing two or more types of fibers. For example, the composite fabric may be woven of threads containing, in a predetermined pattern, threads of polypropylene, nylon, and/or other fibers, such as polyacrylics, natural fibers, etc. With respect to these composite fabrics, there is an immediate problem of finding a dye which will give a union dyeing. This is a problem and a term which is well-known in the art.

Accordingly, another object of this invention is to produce dyes which will dye simultaneously and satisfac torily mixed fabrics composed of more than one synthetic and/ or wool and silk fibers.

A further object of the present invention is to provide dyes which are fast to washing and severe dry cleaning when applied to shaped articles, particularly fibers containing finely dispersed metallic compounds and, more specifically, to provide dyes of extraordinary brilliance and tinctorial value.

One of the very difi'icult problems that has confronted the industry is stabilizing polypropylene and other polyolefin fibers against ageing, that is degradation caused by exposure to air, light, and/ or heat. Many types of known stabilizers have been incorporated into the fibers to impart some degree of stability thereto. However, these stabilizers generally are removed by washing and/ or dry cleaning with various solvents, and the fibers lose most or all of their resistance to ageing.

Accordingly, still another object of this invention .is to stabilize shaped articles formed from polypropylene and other polyolefins and preferably simultaneously stabilize and pigment such materials.

Another object is to improve stability and the resistance of these polymers to ageing, particularly after they have been washed, dry cleaned or exposed to other solvents.

Other objects and advantages of the present invention will appear from the following description.

According to the present invention, it has been found that certain disazo beta-resorcylic acid compounds confer exceptional brilliance and excellent washing and dry 3,251,822 Patented May 17, 1966 cleaning stability when they are dyed on thermoplastic shaped articles of polyolefins, particularly polypropylene containing a metal; polyamides; and polyacrylics. These disazo beta-resorcylic acid compounds are described by the following structural formula:

( a WM:

0 O OH wherein each X is a substituent group attached to the benzene nucleus independently selected from the group consisting of C to C alkyl, cyclo C to C alkyl, carboxyl, nitro, halogen, acyl having up to 6 carbon atoms, benzoyl, N-alkyl sulfonamido said alkyl having 1-5 carbon atoms, N,N-dialkyl sulfonamido each of said alkyls having 15 carbon atoms, alkoxy having 1-4 carbon atoms, trifluoromethyl, cyano, benzoylamino, phenyl amino, carboalkoxy having 1-4 carbon atoms, dialkylamino each of said alkyls having 1-5 carbon atoms, beta cyano ethyl oxy, beta hydroxy ethyl oxy, alkyl sulfonyl having l-4 carbon atoms, hydroxy alkyl sulfonyl having 14 carbon atoms, di (beta hydroxy ethyl) amino, di (beta cyano ethyl amino, 2,3-benz-, and aryl; wherein each Y is a substituent group attached to the benzene nucleus independently selected from the group consisting of C to C alkyl, 2,3-benz, cyclo C to C alkyl, alkoxy having 1-4 carbon atoms, beta hydroxy ethyl oxy, beta cyano ethyl oxy, halogen and trifiuoromethyl; R is a substituent group attached to the benzene nucleus selected from the group consisting of hydrogen and a halogen; a is an integer from 0 to 5 inclusive; and b is an integer from 0 to 4 inclusive. However, other chromophoric substituents for X and Y on the benzene nuclei may also be applicable, e.g., hydroxy, halo alkyl, alkoxy alkyl, cyano alkyl and aryl alkyl.

The foregoing groups on X or Y may be substituted with simple substituents recognized in the dyeing art'such as methyl, nitro, halogen, methoxy and other lower alkoxy groups (containing 1 to 5 carbon atoms), tri fluoromethyl carbonamido, etc.

Preferred disazo beta-resorcylic acid compounds are found among those in which the group or groups X or Y include at least one lower alkyl, that is, 1 to 4 carbon atoms, such as methyl; or such compounds in which the group or groups X or Y include at least one trifluoromethyl group, or at least one halogen (fluorine, chlorine, or bromine), or at least one C to C alkoxy group; or disazo beta-resorcylic acid compounds in which the group or groups X or Y include the 2,3-benz group, such as naphthaleneazobenzeneazo-beta-resorcylic acid; or compounds in which the group or groups X is at least one nitro group.

The desirable properties of the compounds described above are realized by reacting them with a metallic compound of aluminum or zinc. The reaction product is generally formed in the shaped articles, such as fibers OHR 'of polypropylene and other polyolefins, by incorporating initially a metal compound of aluminum of zinc into the polyolefin. This procedure will be described more completely hereafter.

The precise nature and structure of the aforementioned reaction product is not clearly understood. However, it is thought that a chelate ring or linkage may be known prior art procedures.

first place, the metallic compound may not penetrate into all of the interstices of the dye or vice-versa; and, therefore, the reaction may not be complete. In the second place, aluminum and zinc are known to exist in the form of polymers or oligimers; and, therefore, a

. the metal which is finely divided and uniformly distributed throughout the mass. Furthermore, the ratio of fiber to metal is not a critical feature of the invention and a suitable ratio may be readily determined from a given set of circumstances and the desired objectives.

A particularly strikingfeature'of this invention is the stabilizing eifect of the disazo betaresorcylic, acid compounds on the polypropylene or other polyolefin shaped articles, such as a fiber. As stated heretofore, stabilizing such materials has been a very difiicult problem, particularly since laundering, dry cleaning or exposure to other solvents tend to remove known stabilizers. It hasbeen surprisingly found in accordance with the present invention that the disazo beta-resorcylic acid compounds described above irnpart stability to the polypropylene or other polyolefin and resist removal by laundering, dry cleaning, etc.

The aforementioned disazo dyes can be prepared by .various methods. However, they are generally formed by coupling an aminoazo benzene through diazotization with beta-resorcylic acid. The aminoazo benzenes can be provided by rearrangement of a diazoamino compound; by coupling a diazonium compound with an aniline derivative; or by coupling the diazonium compound with an N methane sulfonic acid salt of an aniline derivative. and subsequently hydrolyzing the resulting product with aqueous alkali. However, decarboxylation occurs during the coupling reaction. In order .to obtain outstanding fastness properties, the dyed fiber has to be washed considerably; alternatively, the dyestufi may be purified with sodium carbonate or the like to remove the insoluble decarboxylated by-product.

In one embodiment, a shaped article, for example, a synthetic fiber, has a metal incorporated therein before a disazo betaresorcyclic acid compound is applied. The synthetic fibers or other shaped articles applicable to this invention include polyolefins, polyesters, for example, condensation products of polybasic acids with polyhydric alcohols and Dacron; polyamides, such as nylon; polymers of acrylic acid compounds, such as acrylonitrile; and polymers of vinyl compounds, such as vinyl alcohol, vinyl chloride and styrene. A polyolefin, which is the preferred polymer for a synthetic fiber, includes the following polymers among others: polyethylene, polypropylene, polybutene, poly-3-methyl-butene-l, polypentene, poly-4- methylpentene-l, and polyheptene. The polyolefin, e.g., polypropylene, can be prepared by any known method. A suitable, but not the only method, is disclosedin Belgian Patent No. 533,362, which is incorporated herein by reference.

Synthetic shaped articles are formed from the aforementioned thermoplastic polymers in accordance with A fiber, which is preferred, is defined herein as any fibrous unit, for example, filament yams, rovings,'mats, staple yarns, sheets, rods, plates,

woven fabrics and chopped fibers. The following exemplify specific commercial fibers which can be employed herein: Spun Dacron T-54; Nylon Filament Thread; Cresland T58; Acrilan 1656; and Polypropylene 805 Fiber.

Although synthetic fibers are usually employed, the metallic reaction product embodiment is also applicable to natural fibers, for example, wool, animalized cotton -are suitable dyestuffs. Furthermore, these compounds:

-with a metallic material.

to 20 carbon atoms, which are suitable for this invention,

include aluminum stearate, zinc stearate, aluminum laurate, and the aluminum salt of 2-ethyl hexanoic acid. These salts are intimately dispersed throughout the polymer at any stage prior to its extrusion. blending apparatus is usually adequate to accomplish this result. After dispersion the blend may be extruded at the fluid temperature for the polymer, that is, 250 to 350 C. for polypropylene. Accordingly, the metal is usually distributed uniformly throughout the fiber, such as polyolefin fiber, which provides complete penetration of the dye from the dye bath into the fibers. By way of illustration, the incorporation of the metal salt in the polymer may be made by mixing 10 parts of the powder of the salt with parts of the powder of the polymer to an intimate and uniformly dispersed mixture. This mixture may be extruded to form a concentrate which subsequently is finely divided again and intimately blended with additional polymer to obtain the desired low concentration of metal for extrusion to the shaped product.

The disazo beta-resorcylic acid compounds heretofore described form the basic of an aqueous dye bath into which the fibers are immersed. Since the dyes are insoluble in water, they are dispersed or emulsified in the bath. The concentration of the dye bath can vary over. a wide range, depending upon the depth of shade desired. Any known dyeing technique can be employed in this invention. For example, a skein can be simply immersed into the bath at its approximate boiling temperature; or a finished piece can be dyed by using a jigger. The dye bath can be slightly acidic and the fiber is usually rinsed and dried subsequent to its immersion in the dye bath. Known pressure dyeing techniques which'accelerate the entry of the dye into the fiber may also be used.

In another embodiment of the present invention, the fiber, such as a synthetic or natural fiber, is not modified This unmodified fiber is immersed directly into a dye bath and subsequently rinsed and dried. These steps can be accomplished by any procedure known inthe art and can be similar to the procedures described for the above embodiment. For example, the aqueous dye bath suspension can contain a sulfonated oil, soap, sodium lignin sulfonate, or other suitable dispersing agent. Although direct dyeing operations are generally performed at temperatures of about The fiber to be dyed is usually added to the dye bath' initially at a relatively low temperature and then a higher temperature is provided for carrying out the actual'dyeing operation. The intensity of dyeing is varied by changing the proportion of the weight of dye to the weight of the fiber.

Thus, in accordance with the instant invention, disazo beta-resorcylic acid compounds have been provided which will react with metal-modified shaped articles to form a dyed end product which has excellent brilliance and-tinctorial value and which is also fast to light, dry cleaning and washing. Similarly, these compounds can be applied directly to dye an unmodified fiber since, for example, nylon, polyester, and acrylic fibers have polar groups Aluminum and zinc are the preferred which can form a polar linkage with the present dyes to improve the receptivity of the dye and the rastness properties, such as light fastness of the dye on the fibers.

In still another embodiment of the invention, the disaz'o beta-resorcylic acid compound described above is reacted with the metallic compound in solution withdut' the necessity of any shaped article, such as fiber, being present to form a pigment which can be recovered and used as a pigment in a manner known in the art. The reaction conditions and ratios of reactants in this embodiment of the invention are substantially the same as those described above for the dyeing of fibers. V w

The following examples are submitted to' illustrate but not to limit this invention. Unless otherwise indicated, all parts and percentages in the specifications are based upon weight.

Exahiple I A benzeneazobenzeneazo-beta-resorcylic acid dyestufl wasprovided by dissolving 92.2 parts (.6 mol) of betaresorcylic acid in 1800 parts of water containing 160 parts (2.4 mols) of sodium acetate. This first solution was cooled to C.

A separate second solution was prepared by su'spending at 70 C. 145 parts (.6 mol) of aminoazobenzene hydrochloride in 2400 parts of water containing 113 parts (1.2 mols) of concentrated hydrochloric acid. After stirring, slowly cooling to 30 C., and cooling subsequently with iceto 10 C., 225 parts (.65 mol) of a 20% sodium nitrite solution was added thereto over a 30 minute period. A diazo second solution was formed after stirring for one hour and subsequently clarifying by filtration.

Over a period of three hours, the diazo second solution was added to the first solution. After the coupling was complete, the pH was adjusted to 7 and the dyestuif reaction product therefrom was filtered. The insoluble dyestuif presscake was subsequently slurried at 70 C. in 10,000 parts water and 60 parts of sodium hydroxide. The dissolved dyestuflt' was then filtered hot to remove the insoluble carboxylated by-products. The pure dyestuff from the filtrate was isolated with suflicient acid to provide a pH of 7. After filtering, the dyestutf was dispersed to a 10% aqueous paste.

Fiber grade polypropylene, which was blended intimately and uniformly with 0.080 wt. percent of aluminum monostearate, was used to manufacture 4 /2 denier crimped staple fiber by melt extruding, stretching, crimping and cutting to a 2 in. length. This cut fiber was subsequently carded and spun to produce yarns approxi -mating .10s single (cotton system) count.

Convenient sized skeins were then reeled from this yarn.

A sample containing ten grams of skein was provided. This sample was'immersed in a 500 cc. dye bath at 120 F. The bath consists of an aqueous dispersion of 0.6 gram of the dry aforementioned dyestuff. Prior to the entry of the yarn, sufiicient acetic acid was added to the dye bath to provide a pH of 6.0. The dyeing was accomplished by gradually raising the temperature of the dye bath to its boiling point during a 30 minute period. The skein was frequently turned with a glass stirring rod and the temperature was maintained at 212 F. for aperiod of one hour. The yarn was then removed from the dye bath and thoroughly rinsed in running Water at 160 F. The skein was subsequently scoured by turning it for 30 minutes at 160 F. in a 400 cc. aqueous bath containing /2% of triton X-lOO (iso-octyl-phenyl poly ethoxy ethanol) and /2% of sodium carbonate. A thorough rinse was subsequently performed in running water at 110 F.

The dyed sample Was then subjected to the following tests.

1) Color fastness to dry cleaning..Tentative Test Method 851960 (1960 Technical Manual of the American Association of Textile Chemists and Colorists, pages 88-9) amended as follows; the temperature shall be 115 F.; the time shall be 1 hour; and the amount of perchlorethylene shall be 200 cc.

(2) Colorjdstness to washing (polypropyler l'e) .Ten- 5 tative Test Method 61-1960, test number III-A 1960 Technical Manual of the American Association of Textile Chemists and Colorists, pages 93-4). In each instance, the dyeings shall rate (for polypropylene) as follows: for color loss, class 5; for staining, class 3 or better. (3) Color) fdstness for washing (ryn'the'ties).-AATCC tentativetest method 6I-1961T (page 105 loc. cit.) with Test III-A being used for polyester and after-chromed nylon and Test II-A for nylon. V, I v

(4) Color fairness to light TCC Standard Test Method 1 6 A-l960' (page 9010c. cit.

(5) Color fastr'tess t 0 oxides of nitrogen in the almosp'here (g'as iriding'L-Three cycles were used of Standard Test Method 234 957 (page 9 8 loc.cit.) or Standard Test Method 75''1956 (page 100 loc. cit).

Q Sublimation and heat faslness tests-Sublimation and heat fastnesstests were run at 265 F. for minutes.

The dyed polypropylene herein had a yellow or orange hue and possessed excellent fastness properties to wash ing, dry cleaning, gas fading, sublimation and light.

Example 11 A Dacron fiber was dyed with the dyestuif of Example I by providing a bath of 180 F. containing 200 parts water and 1.5 parts of a blend of 67% biphenyl and 33% anionic emulsifier. Ten grams of skein were incorporated for a five-to-ten minute run. The aforementioned dye, which had been previously pasted and dispersed in 100 parts water, was added and the temperature of the bath was raised to boil for 1 to 1 /2 hours. The following procedures were subsequently employed: rinsing for 5 minutes in a fresh bath heated as rapidly as possible to 190 to 200 F.; dropping without cooling; and scouring at 200 F. for 15 to minutes.

The dyed Dacron fiber was a brilliant yellow or orange and it had excellent fastness to washing, dry cleaning and light.

Example III The dye compounds indicated in Table I include the dye described in the previous examples andthose dyes which were prepared by similar procedures with the reactants being varied to form the desired end product. Polypropylene and Dacron fibers were dyed with certain of these compounds as per Example I or II and the re sultant shades are also indicated in Table 1.

a 2 a 2 j 0011 TABLE 1 A-Ring Substit- B-Riug Substituents uents Shade on Polypro pylene Shade on Dacron Yellow or Orange. Yellow Orange.

Yellow or Orange. Yellow Orange. Rusty Orange. Salmon.

4-NO 2,3-Ben1 4-N0z; 2,6 di-Cl 2,5-di-OH O Z-NO: 2,3-Benz Red Brown.

Having set forth the general nature and specific embodiments of the present invention, the scope is now particularly pointed out in the appended claims.

We claim: 1 1. A dye composition having the structure:

( JOOH wherein each X is a substituent group attached to the benzene nucleus independently selected from the group consisting of lower alkyl, carboxyl, nitro, chlorine, bromine and fluorine; wherein each Y is a substituent group attached to the benzene nucleus independently selected from the group consisting of lower alkyl, 2,3-benz, alkoxy having 1-4 carbonatoms; a is an integer from to 3 inclusive; and b is an integer from 0 to 2 inclusive.

2. A dye composition which is 4-nitro-2,6-dichlorobenzeneazo 2,5 dirnethoxybenzeneazo beta resorcylic acid.

3. A dye composition which is benzeneazobenzeneazobeta-resorcylic acid.

4. A dye composition which is 3-methylbenzeneazo-3- methylbenzeneazo-beta-resorcylic acid.

5. A dye composition which is 4-nitrobenzeneazobenzeneazo-beta-resorcylic acid.

6. A dye composition which is 3-nitrobenzeneazobenzeneazo-beta-resorcylic acid.

7. A dye composition which is benzeneazonaphthaleneazo-beta-resorcylic acid. i

8. A dye composition which is 4-nitrobenzeneazonaphthaleneazo-beta-resorcylic acid.

9. A dye composition which is 2-nitrobenzeneazonaphthaleneazo-beta-resorcylic acid.

10. A dye composition which is 4ca'rboxy-lbenzeneazobenzeneazo-beta-resorcylic acid.

References Cited by the Examiner UNITED STATES PATENTS 431,297 7/1890 Walter 260 207 528,965 11/1894 Muhlert 260'207 1,264,604 4/1918 BOhn 260 148 1,310,532 7/1919 Jones 260-187 1,557,265 10/1925 Miller 260 187 2,080,191 5/1937 Straub et a1. 260-148 2,096,722, 10/1937 Anderson 260-148 2,867,494 1/1959 1 Streck 8 -42 2,938,814 7/1959 Streck 842, 3,096,140 7/1963 Gaetani 260 174 X FOREIGN PATENTS 551,437 2/1943 Great Britain.

CHARLES B. PARKER, Primary Examiner. ABRAHAM H. WINKELSTEIN, Examiner. 

1. A DYE COMPOSITION HAVING THE STRUCTURE: 